CN114308049A - Growth catalyst for preparing carbon nano tube with high specific surface area - Google Patents

Growth catalyst for preparing carbon nano tube with high specific surface area Download PDF

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CN114308049A
CN114308049A CN202111554506.3A CN202111554506A CN114308049A CN 114308049 A CN114308049 A CN 114308049A CN 202111554506 A CN202111554506 A CN 202111554506A CN 114308049 A CN114308049 A CN 114308049A
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catalyst
carbon nanotube
carbon
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张新杰
李卫力
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Nori Shenzhen New Technology Co ltd
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Abstract

The invention discloses a growth catalyst for preparing carbon nanotubes with high specific surface area. In a first aspect of the present application, there is provided a carbon nanotube growth catalyst, comprising FexCoyMozAl is 0.3-0.6, 5-20, and x-y. The carbon nanotube growth catalyst according to the embodiment of the application has at least the following beneficial effects: the Fe-Co-Mo-Al quaternary carbon nanotube growth catalyst provided by the embodiment of the invention comprises multiple components of iron, cobalt, molybdenum and aluminum, the catalyst can be directly used without high-temperature pretreatment, and the catalyst can be used for producing the catalyst with the specific surface area of more than 350m at a high rate2The/g carbon nano tube has excellent catalytic growth effect and has larger application prospect in the preparation of the carbon nano tube.

Description

Growth catalyst for preparing carbon nano tube with high specific surface area
Technical Field
The application relates to the technical field of carbon nanotubes, in particular to a growth catalyst for preparing carbon nanotubes with high specific surface area.
Background
Carbon Nanotubes (CNTs) are one-dimensional nanocarbon materials with a hollow tubular structure, consisting of carbon atoms arranged in a hexagonal lattice, having a diameter of about 1 to 100nm and a high aspect ratio. Theoretically, carbon nanotubes have superior tensile strength, excellent thermal conductivity, excellent electrical conductivity, and chemical stability. Due to its excellent physical and chemical properties, CNTs exhibit potential applications in the fields of composite materials, new energy, aerospace, biotechnology, electronics, semiconductors, and the like, and have been widely and deeply studied. Over the years of development, CNTs have achieved commercial applications in conductive plastics and battery conductive additives.
The synthesis method of the CNT mainly includes an arc discharge method, a laser evaporation method, and a chemical vapor deposition method. Among them, the arc discharge method and the laser evaporation method are not suitable for mass production of CNTs due to cost and equipment limitations, and in contrast, the chemical vapor deposition method becomes a main process for producing large-tonnage carbon nanotubes, and the specific methods of the chemical vapor deposition method are as follows: organic small molecules (such as ethylene, propylene, ethanol and the like) are catalyzed by a transition metal catalyst under the high-temperature condition to crack and deposit solid carbon nanotubes, hydrogen and the like.
CNTs can be classified into three types according to the number of tube walls: single-walled CNTs having a diameter of about 1 nm; double-walled CNTs having a diameter of about 1.4-3 nm; and multi-walled CNTs having a diameter of about 5 to 100 nm. In the process of multi-walled CNT synthesis, the problem is that as the number of walls of the multi-walled carbon nanotubes increases, the proportion of disordered graphite also increases, resulting in a decrease in the quality of the multi-walled carbon nanotubes. For this reason, the industry has been striving to reduce the number of walls of multi-walled CNTs and increase their specific surface area. In view of the preparation process of chemical vapor deposition, the transition metal catalyst has an important effect on the growth and structural control of CNTs, and thus, it is necessary to provide a growth catalyst capable of increasing the specific surface area of carbon nanotubes.
Disclosure of Invention
The present application is directed to solving at least one of the problems in the prior art. To this end, the present application proposes a growth catalyst capable of increasing the specific surface area of the carbon nanotube.
In a first aspect of the present application, there is provided a carbon nanotube growth catalyst, comprising FexCoyMozAl is 0.3-0.6, 5-20, and x-y.
The carbon nanotube growth catalyst according to the embodiment of the application has at least the following beneficial effects:
the Fe-Co-Mo-Al quaternary carbon nanotube growth catalyst provided by the embodiment of the invention comprises multiple components of iron, cobalt, molybdenum and aluminum, the catalyst can be directly used without high-temperature pretreatment, and the catalyst can be used for producing a specific surface area larger than 350m at a high rate during chemical vapor deposition2The/g carbon nano tube has excellent catalytic growth effect and has larger application prospect in the preparation of the carbon nano tube.
In a second aspect of the present application, there is provided a method for preparing a carbon nanotube growth catalyst, the method comprising the steps of:
providing a metal precursor solution, wherein the metal precursor solution comprises an iron source, a cobalt source, a molybdenum source and an aluminum source according to the stoichiometric ratio, and the stoichiometric ratio is required as follows: based on the molar weight of aluminum as 1, the molar weight of iron is x, the molar weight of cobalt is y, the molar weight of molybdenum is z, 0.3 to (x + y) to 0.6, 5 to (x + y)/z is 20, and x is less than or equal to y;
and mixing the metal precursor solution with a precipitator for reaction, and collecting the precipitate to obtain the carbon nano tube growth catalyst.
Wherein the metal precursor solution is a raw material solution containing the metal elements required by the carbon nanotube growth catalyst, and comprises FexCoyMozX represented by Al: y: z: 1, mixing the precursor solution and a precipitator to perform coprecipitation reaction, wherein metal elements are hydrolyzed to form precipitates, thereby obtaining the carbon nano tube growth catalyst. The precipitant is optionally capable of performing a coprecipitation reaction with the metal precursor solution, and includes but is not limited to at least one of ammonia, ammonium carbonate, ammonium bicarbonate, urea, ammonium fluoride, and the like.
It can be seen that the preparation method of the carbon nanotube growth catalyst provided in the embodiment of the present application selects multiple components including iron, cobalt, molybdenum and aluminum as raw materials, can complete the preparation without adding complexing agent and surfactant, has a simpler process, is beneficial to large-scale production, and can realize high-yield production of carbon nanotubes with large specific surface area by using the prepared growth catalyst.
It can be understood that the metal source and the precipitant are subjected to precipitation reaction to directly form hydroxide, and considering the chemical vapor deposition process for preparing the carbon nanotube, the five-membered metal hydroxide can actually be calcined and reduced under the high-temperature condition of vapor deposition to form a mixture or alloy of elementary substances of the five-membered metal to participate in the catalytic reaction. Therefore, the step of calcination reduction may be omitted or retained during the preparation of the catalyst. If the step of roasting reduction needs to be reserved, roasting can be carried out at 400-800 ℃, and further roasting is carried out at 400-700 ℃, 500-700 ℃ and 600-700 ℃.
In some embodiments of the present application, 0.3 ≦ (x + y) 0.5, or 0.375 ≦ (x + y) 0.6, or 0.375 ≦ (x + y) 0.5.
In some embodiments of the present application, 5 ≦ (x + y)/z ≦ 15, or 8 ≦ (x + y)/z ≦ 12, or (x + y)/z is about 10.
It will be appreciated that the above requirements for the stoichiometric ratios of x and y, and for the stoichiometric ratios of x, y and z, may be combined arbitrarily therefrom.
In some embodiments of the present application, the iron source, the cobalt source, and the aluminum source are each independently selected from the group consisting of nitrate, sulfate, chloride, and acetate.
In some embodiments of the present application, the molybdenum source is a molybdate salt including, but not limited to, at least one of ammonium molybdate, ammonium heptamolybdate.
In some embodiments of the present application, the precipitating agent is selected from at least one of ammonium carbonate, ammonium bicarbonate, and aqueous ammonia.
In some embodiments of the present application, the precipitant has a concentration of 1 to 4 mol/Kg.
In some embodiments of the present disclosure, the reaction temperature after adding the precipitant is 20 to 100 ℃, preferably 20 to 80 ℃, and 30 to 60 ℃.
In some embodiments of the present application, the precipitate is collected by filtering the precipitate and drying the filtered precipitate at a temperature of 80 to 200 ℃.
In a third aspect of the present application, there is provided a method for preparing a carbon nanotube, the method comprising the steps of:
and under the protective atmosphere, carrying out chemical vapor deposition on a carbon source under the action of a metal catalyst to obtain the carbon nanotube, wherein the metal catalyst is the carbon nanotube growth catalyst or the carbon nanotube growth catalyst prepared by the preparation method.
In some embodiments of the present application, the carbon source is an optional carbon source material in the form of a reaction gas, including but not limited to hydrocarbons in a gas phase at normal temperature, such as at least one of methane, ethane, ethylene, propane, propylene, acetylene, and the like. In some preferred embodiments, the carbon source is ethylene or propylene. It is understood that other commonly used carbon sources such as ethanol, acetone, dimethyl ether, etc. may also be used as the carbon source required in the preparation process.
In some embodiments of the present application, the reaction temperature of the chemical vapor deposition is 600 to 700 ℃, and more preferably 630 to 650 ℃; the reaction time of the chemical vapor deposition is 10 to 30 minutes, and more preferably 15 to 20 minutes.
In some embodiments of the present application, the protective atmosphere refers to protection from air, oxygen, and the like by inert gas, nitrogen, and the like, so as to avoid affecting the growth of the carbon nanotubes.
In a fourth aspect of the present application, there is provided a carbon nanotube produced by the foregoing production method. The carbon nanotubes prepared by the method have a particle size of at least 350m2The BET specific surface area/g shows that the aggregation form of the carbon nanotube is a twisted form when observed under a mirror, and the carbon nanotube has excellent properties in various aspects based on its high specific surface area.
In a fifth aspect of the present application, there is provided a composition comprising the aforementioned carbon nanotubes. The composition is formed by using the carbon nano tube as a main raw material or an additive component, including but not limited to conductive paste, an additive, a lubricant and the like.
The application aims at a four-component carbon nanotube growth catalyst and a specific surface larger than 350m2A winding type carbon nanotube in terms of/g. By optimizing the proportion relation of the components of the Fe-Co-Mo-Al catalyst and the generation of the carbon nano tubeThe carbon nanotubes with large specific surface area can be prepared with high yield for a long time and at high temperature, and can be used as a polymer conductive additive and a lithium ion battery anode conductive agent.
Additional aspects and advantages of the present application will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the present application.
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FIG. 1 is a scanning electron microscope image of carbon nanotubes grown at 620 ℃ for 10 minutes in example 1 of the present invention.
FIG. 2 is a scanning electron microscope image of carbon nanotubes grown at 640 ℃ for 10 minutes in example 2 of the present invention.
FIG. 3 is a transmission electron microscope image of carbon nanotubes grown at 640 ℃ for 10 minutes in example 2 of the present invention.
Detailed Description
The conception and the resulting technical effects of the present application will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, and not all embodiments, and other embodiments obtained by those skilled in the art without inventive efforts based on the embodiments of the present application belong to the protection scope of the present application.
The following detailed description of embodiments of the present application is provided for the purpose of illustration only and is not intended to be construed as a limitation of the application.
In the description of the present application, the meaning of a plurality is one or more, the meaning of a plurality is two or more, and the above, below, exceeding, etc. are understood as excluding the present number, and the above, below, within, etc. are understood as including the present number. If the first and second are described for the purpose of distinguishing technical features, they are not to be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated. About is understood to mean floating up and down within the range of + -20%, + -15%, + -10%, + -8%, + -5%, + -3%, + -2%, + -1%, + -0.5%, + -0.2%, + -0.1% of the point values.
In the description of the present application, reference to the description of the terms "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Example 1
The embodiment provides a Fe-Co-Mo-Al quaternary carbon nanotube growth catalyst, and the preparation method comprises the following steps:
(1) taking Fe (NO)3)3·9H2O、Co(NO3)2·6H2O and Al (NO)3)3·9H2O is respectively dissolved in deionized water to prepare 1mol/Kg solution for later use. To obtain (NH)4)6Mo7O24·4H2Dissolving O in deionized water to prepare 0.1mol/Kg solution for later use. To obtain (NH)4)2CO3Dissolving in deionized water to prepare 2mol/Kg solution for later use.
(2) According to the element mole ratio of Fe: co: mo: al ═ 0.25: 0.25: 0.05: and 1, respectively weighing 20g, 40g and 80g of Fe, Co, Mo and Al precursor solutions, and mixing to obtain the metal precursor solution.
(3) A2L three-necked flask was charged with 200mL of deionized water and 150g of the prepared (NH)4)2CO3Stirring the solution, heating to 45 ℃, and slowly dripping the metal precursor solution. After the end of the dropwise addition, stirring was continued for half an hour, and the final pH was measured to be 8-8.5 using pH paper. Filtering to obtain a precipitate, washing the precipitate without deionized water, drying the precipitate in a drying oven at 120 ℃ for 24 hours, and grinding the dried product into fine powder to obtain the Fe-Co-Mo-Al quaternary carbon nanotube growth catalyst.
The embodiment also provides a carbon nanotube, and the preparation method of the carbon nanotube comprises the following steps:
carbon nanotube growth experiments were performed in a horizontal fixed bed quartz reactor. The carbon nanotube growth catalyst prepared in this example was uniformly placed in a quartz boat, and the quartz boat was then pushed into the constant temperature zone of the tube furnace. The temperature was raised to the reaction temperature under nitrogen atmosphere, and then ethylene was introduced as a carbon source. And stopping introducing ethylene after reacting for a period of time, taking out the carbon nano tube after the temperature is reduced to room temperature in the nitrogen atmosphere, weighing, calculating the multiplying power, and measuring the specific surface area by a BET method.
According to the above preparation method, with different reaction temperatures and reaction times, the detection results of the finally prepared carbon nanotubes are shown in table 1:
TABLE 1 production rate and specific surface area results of carbon nanotubes under different experimental conditions of example 1
Experimental number Reaction temperature/. degree.C Reaction time/min Production multiplying power Specific surface area/(m)2/g)
1 600 10 14 344
2 610 10 16 352
3 620 10 19 362
4 620 15 24 351
5 630 10 22 356
6 640 10 25 355
7 660 10 35 345
Wherein, the production rate ═ (total weight of CNTs after reaction-weight of pre-reaction catalyst)/weight of pre-reaction catalyst;
the specific surface area of the CNTs was measured by the BET method. A larger BET specific surface area indicates that the CNT has a smaller diameter. When used as a conductive additive, CNTs with large specific surface area are added in a smaller amount.
Referring to fig. 1, it is an electron microscope image of the carbon nanotubes grown at 620 ℃ for 10 minutes in the above table, and it can be seen from the electron microscope image that the carbon nanotubes prepared in the examples of the present application have a significant "winding type" secondary aggregation morphology.
Referring to the detection results in Table 1, the specific surface area of more than 350m can be obtained within the reaction temperature of 610-640 DEG C2(ii) CNT in g. On the other hand, comparing the growth rates, it was found that the growth rate of CNTs gradually increased with increasing temperature; meanwhile, the growth rate of the carbon nano tube can reach 25 after 10 minutes of reaction time.
The specific surface area of the CNT and the number of the tube walls thereof have a direct relationship with the tube diameter, and the smaller the tube walls, the larger the specific surface area. The number of walls and the diameter of the tube are related to the particle size of the active component particles of the catalyst, and the smaller the particle size, the smaller the number of the walls of the obtained CNT, the smaller the tube diameter and the larger the specific surface area. The initial particle size of the catalyst active component particles is determined by a catalyst preparation method, but in the process of preparing the CNT by chemical vapor deposition, the particle size of the catalyst active component particles can grow gradually along with the reaction at a higher reaction temperature, so that the number of the CNT walls is increased, and the tube diameter is enlarged until the catalyst is deactivated; lowering the reaction temperature can slow down the growth of catalyst particles, but the contradiction is that the reduction of the reaction temperature leads to a slow growth rate of CNTs and a reduction in production efficiency. The catalyst prepared by the embodiment can reach the growth rate of about 25 at lower temperature in a shorter time, and simultaneously maintains the high specific surface area of the CNT.
Example 2
The embodiment provides a Fe-Co-Mo-Al quaternary carbon nanotube growth catalyst, the preparation method of the catalyst is the same as that of embodiment 1, the molar ratio of elements is Fe: co: mo: al 0.125: 0.25: 0.0375: 1.
the experimental results of the carbon nanotubes prepared by the preparation method of example 1 using the above carbon nanotube growth catalyst at different reaction temperatures and reaction times are shown in table 2:
TABLE 2 production rate and specific surface area results of carbon nanotubes under different experimental conditions of example 2
Experimental number Reaction temperature/. degree.C Reaction time/min Production multiplying power Specific surface area/(m)2/g)
1 620 10 8.5 368
2 630 10 11 368
3 640 10 12 374
4 650 10 13 374
5 660 10 17 369
6 700 10 23 347
Referring to fig. 2 and 3, which are scanning electron microscope and transmission electron microscope images of carbon nanotubes grown at 640 ℃ for 10 minutes, it can be seen from fig. 2 that the carbon nanotubes prepared in this example are also "winding type". Referring to fig. 3, the diameter of the carbon nanotube prepared in example 2 of the present application is 10 to 20nm, wherein it can be clearly seen that the multi-layer structure is a typical multi-wall carbon nanotube, and the number of walls is approximately 8 or more.
Combining the results of Table 2 and Table 1, the production rate decreased with increasing the Co element ratio, but the specific surface area of the obtained CNT reached 370m, as compared with example 12And about/g.
Comparative example 1
The comparative example provides a quaternary carbon nanotube growth catalyst of Fe-Co-Mo-Al, which is different from that of example 1 in that the element molar ratio is Fe: co: mo: al ═ 0.25: 0.125: 0.0375: 1.
the experimental results of the carbon nanotubes prepared by the preparation method of example 1 using the above carbon nanotube growth catalyst at different reaction temperatures and reaction times are shown in table 3:
TABLE 3 production rate and specific surface area results of carbon nanotubes in different experimental conditions of comparative example 1
Figure BDA0003418240300000061
Figure BDA0003418240300000071
Compared with the embodiment 2, the comparative example 1 has the advantages that the molar ratio of Fe to Co is changed, so that the proportion of Fe is larger than that of Co, the specific surface area of the finally prepared CNT is lower, and is reduced by 50-70 m2/g。
Comparative example 2
The comparative example provides a Fe-Co-Mn-Mo-Al five-membered carbon nanotube growth catalyst, which is different from the catalyst in example 1 in that the element molar ratio is Fe: co: mn: mo: al ═ 0.3: 0.3: 0.09: 0.06: 1.
the experimental results of the carbon nanotubes prepared by the preparation method of example 1 using the above carbon nanotube growth catalyst at different reaction temperatures and reaction times are shown in table 4:
TABLE 4 production rate and specific surface area results of carbon nanotubes in different experimental conditions of comparative example 2
Experimental number Reaction temperature/. degree.C Reaction time/min Production multiplying power Specific surface area/(m)2/g)
1 620 10 13 303
2 640 10 20 300
3 660 10 17 279
Comparative example 2 compared with example 1, additional Mn element was added, but the specific surface area of the carbon nanotube prepared under the same conditions with the catalyst was still only 300m2The/g is even insufficient, and the reduction is obvious.
Comparative example 3
The comparative example provides a quaternary carbon nanotube growth catalyst of Fe-Co-Mo-Al, which is different from that of example 1 in that the element molar ratio is Fe: co: mo: al 0.125: 0.125: 0.025: 1.
the experimental results of the carbon nanotubes prepared by the preparation method of example 1 using the above carbon nanotube growth catalyst at different reaction temperatures and reaction times are shown in table 5:
TABLE 5 production rate and specific surface area results of carbon nanotubes in comparative example 3 under different experimental conditions
Experimental number Reaction temperature/. degree.C Reaction time/min Production multiplying power Specific surface area/(m)2/g)
1 620 10 3.2 300
2 640 10 4 318
3 660 10 5.4 316
4 680 10 4.9 290
The contents of Fe and Co in the catalyst of this comparative example were greatly reduced as compared with example 1, and the final catalyst was obtainedThe obtained CNT, like the other comparative examples, was still only 300m2About/g, the quality requirement of the high-quality multi-wall carbon nano-tube cannot be met.
It can be seen from the combination of the above test results of the examples and the comparative examples that the carbon nanotube growth catalyst disclosed in the examples of the present application is made of FexCoyMozAl, four elements. The catalyst can be prepared by coprecipitation reaction of a metal precursor solution and an alkali solution. When the proportion of each element satisfies the conditions of 0.3-0.6, 5-20, x-20, the specific surface area of the carbon nano tube obtained by the catalyst prepared by the catalyst preparation method participating in the chemical vapor deposition can reach 350m2More than g, the carbon nano tube belongs to winding type carbon nano tube. The carbon nano tube with high specific surface area can be used as a polymer conductive additive and a lithium ion battery positive electrode conductive agent, so that the battery performance is improved.
The present application has been described in detail with reference to the embodiments, but the present application is not limited to the embodiments described above, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present application. Furthermore, the embodiments and features of the embodiments of the present application may be combined with each other without conflict.

Claims (10)

1. A carbon nanotube growth catalyst characterized by FexCoyMozAl is 0.3-0.6, 5-20, and x-y.
2. The preparation method of the carbon nano tube growth catalyst is characterized by comprising the following steps:
providing a metal precursor solution, wherein the metal precursor solution comprises an iron source, a cobalt source, a molybdenum source and an aluminum source according to a stoichiometric ratio, and the stoichiometric ratio is required as follows: based on the molar weight of aluminum as 1, the molar weight of iron is x, the molar weight of cobalt is y, the molar weight of molybdenum is z, 0.3 to (x + y) to 0.6, 5 to (x + y)/z is 20, and x is less than or equal to y;
and mixing the metal precursor solution with a precipitator for reaction, and collecting the precipitate to obtain the carbon nano tube growth catalyst.
3. The method according to claim 2, wherein the precipitant is at least one selected from the group consisting of ammonium carbonate, ammonium bicarbonate, and ammonia water.
4. The method of claim 2, wherein the iron, cobalt and aluminum sources are each independently selected from the group consisting of nitrate, sulfate, chloride and acetate.
5. The method of claim 2, wherein the molybdenum source is a molybdate.
6. The preparation method according to claim 2, wherein the reaction temperature after the precipitant is added is 20 to 100 ℃.
7. The method according to claim 2, wherein the precipitate is collected by filtering the precipitate and drying the filtered precipitate at a temperature of 80 to 200 ℃.
8. The preparation method of the carbon nano tube is characterized by comprising the following steps:
performing chemical vapor deposition on a carbon source under the action of a metal catalyst under a protective atmosphere to obtain the carbon nanotube, wherein the metal catalyst is the carbon nanotube growth catalyst in claim 1 or the carbon nanotube growth catalyst prepared by the preparation method in any one of claims 2 to 7.
9. A carbon nanotube produced by the production method according to claim 8.
10. A composition comprising the carbon nanotubes of claim 9.
CN202111554506.3A 2021-12-17 2021-12-17 Growth catalyst for preparing carbon nano tube with high specific surface area Pending CN114308049A (en)

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
CN115536007A (en) * 2022-10-31 2022-12-30 山东大展纳米材料有限公司 Few-wall array carbon nanotube and growth catalyst precursor and preparation method thereof
CN115608372A (en) * 2022-09-15 2023-01-17 河南国碳纳米科技有限公司 Iron-cobalt-based catalyst, carbon nano tube and preparation process thereof
CN115650211A (en) * 2022-09-15 2023-01-31 河南国碳纳米科技有限公司 Carbon nano tube and two-section type preparation process thereof
CN115672327A (en) * 2022-11-10 2023-02-03 无锡碳谷科技有限公司 High specific surface area superfine nano catalyst and preparation method and application thereof

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CN103827027A (en) * 2012-01-11 2014-05-28 Lg化学株式会社 Carbon nanotubes and method for manufacturing same

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
CN103827027A (en) * 2012-01-11 2014-05-28 Lg化学株式会社 Carbon nanotubes and method for manufacturing same

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115608372A (en) * 2022-09-15 2023-01-17 河南国碳纳米科技有限公司 Iron-cobalt-based catalyst, carbon nano tube and preparation process thereof
CN115650211A (en) * 2022-09-15 2023-01-31 河南国碳纳米科技有限公司 Carbon nano tube and two-section type preparation process thereof
CN115608372B (en) * 2022-09-15 2024-03-26 河南国碳纳米科技有限公司 Iron-cobalt-based catalyst, carbon nanotube and preparation process thereof
CN115536007A (en) * 2022-10-31 2022-12-30 山东大展纳米材料有限公司 Few-wall array carbon nanotube and growth catalyst precursor and preparation method thereof
CN115536007B (en) * 2022-10-31 2024-02-20 山东大展纳米材料有限公司 Few-wall array carbon nano tube, growth catalyst precursor thereof and preparation method
CN115672327A (en) * 2022-11-10 2023-02-03 无锡碳谷科技有限公司 High specific surface area superfine nano catalyst and preparation method and application thereof

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